Based on water chemistry data, a rockfill dam in South Korea was investigated to identify major parts of substantial dam water leakage. Sinkholes in the dam crest and abnormal water leakage through the dam were observed since the first impounding of the dam. Previous investigations, including observational drillings, hydraulic tests, geophysical surveys, and tracer tests, revealed the development of a high permeability zone in the clay core and an abnormally high phreatic line zone in the left embankment. Sequential tracer tests provided further evidence of locations of preference and rapid water leakage pathways. In this study, we examined the usefulness of water chemistry data to confirm previous findings of water leakage. Factor analysis of the water chemistry data revealed major processes controlling the chemical composition, which include the wash-out and successive dissolution of fill materials in the dam interior, interaction between percolating water and dam core materials, and contamination of seeping water by grouting materials and previous tracer tests. Distinct spatial distribution of similar chemical groups was illustrated by cluster analysis and confirmed the location of major water leakage at the left abutment adjoining the spillway.